Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D1/00—Evaporating
  • B01D1/02—Evaporators with heating coils
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
  • C08G69/14—Lactams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/28—Preparatory processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids

Definitions

• From the DD patent specification 110,507 is a process for the preparation of copolyamides of caprolactam and salts of diamines and dicarboxylic acids, eg. As AH salt, in which one feeds a VK tube from above caprolactam, AH salt and water and removes the corresponding copolyamide at the bottom.
• the method has the disadvantage that with the escaping at the top of the VK tube vapors diamine is discharged and lost. Furthermore, the method has the disadvantage that a precise temperature control in the VK tube head is considerably impaired by the released water with the supplied AH salt solution.
• the vapor phase is separated from the prepolymer melt and passed to a column where water vapor and an aqueous diamine solution are separated and the diamine-containing aqueous solution is recycled to the polymerization. Subsequently, the prepolymer melt is mixed with molten caprolactam and the mixture of prepolymer and caprolactam is passed from top to bottom through a vertical polymerization tube to obtain a copolyamide.
• the prepolymer from the precondensation zone already consists of blocks of low molecular weight condensed diamines and dicarboxylic acids, which are still retained as blocks in the subsequent polymerization with caprolactam. A better statistical distribution of the components no longer takes place. More salt is needed from diamines and dicarboxylic acids to arrive at the desired copolymer melting point. In addition, copolymers produced in this way tend more to discoloration.
• the process according to the invention has the advantage that it gives copolyamides whose co-monomer constituents are distributed significantly more statistically in the polymer chain than is possible by known processes. This can reduce the proportion of salts of diamines and dicarboxylic acids compared to conventional methods.
• the new process has the advantage that the copolyamides thus produced are distinguished by improved product properties (eg lower intrinsic color).
• helical tube evaporators in the production and processing of polymers is known per se.
• the WO 2008/049786 describes the use of helical tube evaporators in the production of polyamides.
• the helical tube evaporators are used for the concentration of aqueous extract solutions from the extraction of polyamides based on polyamide-6.
• a helical tube evaporator in polyamide production FR-A-2 914 308 , In the process described therein, the polycondensation takes place for the most part in a helical tube, which is followed by a vaporization chamber for the separation of gaseous constituents and subsequent tube reactor.
• the pressure at the outlet of the helical tube evaporator is more than atmospheric pressure, preferably more than 0.5 MPa, more preferably more than 1.0 MPa.
• the discharge from the helical tube evaporator is fed to a device in which at least part of the vapor fraction is removed. In this chamber, the vapor phase is separated from the liquid phase, which settles to the bottom.
• the chamber is also operated at a higher pressure than atmospheric pressure, preferably between 0.5 and 2.5 MPa.
• step 3 Only at this stage joins a tubular reactor, which is to serve for pressure reduction (step 3). It should be a non-adiabatic pressure reduction, so that a pressure in the vicinity of the atmospheric pressure is obtained.
• the EP-B-1 113 848 relates to methods for evaporating polymer solutions of thermoplastic polymers. It polymer solutions are concentrated with a polymer content of 5 to 20 wt .-% in a sequence of Sch GmbHrohrverdampfer downstream tube bundle heat exchangers with downstream separator.
• the EP-B-1 173 264 relates to a method and apparatus for evaporating polymer solutions of thermoplastic polymers. It is also a polymer solution having a polymer content of 5 to 20 wt .-% concentrated in a sequence of Schlenk tube evaporator with downstream separator and subsequent shell and tube heat exchanger with downstream separator.
• the EP-B-1 007 582 relates to processes for the preparation of polyamide prepolymers in which a prepolymerization is carried out in the presence of a flowing vapor phase.
• Lactamkomponenten those having 6 to 12 ring members such.
• the copolyamide components used are salts of, preferably equimolar, amounts of diamines and dicarboxylic acids in aqueous solution.
• Preferred diamines have the formula I. H 2 NR 1 -NH 2 I, in which R 1 denotes an alkylene radical having 4 to 16 carbon atoms, in particular 4 to 8 carbon atoms, which may have a cycloalkylene radical, or a 1,3- or 1,4-phenylene radical.
• Suitable compounds are, for example, 1,4-diaminobutane, hexamethylenediamine, octamethylenediamine, decamethylenediamine, or 1,3-phenylenediamine or 1,4-phenylenediamine.
• Preferred dicarboxylic acids have the formula II HOOC-R 2 -COOH II, in which R 2 denotes an alkylene radical having 4 to 12 carbon atoms, in particular 4 to 8 carbon atoms, which may have a cycloalkylene radical, or denotes a 1,3- or 1,4-phenylene radical.
• Suitable dicarboxylic acids are, for example, adi-adipic acid, Azelaic acid, sebacic acid, suberic acid, dodecanedioic acid, or terephthalic acid or isophthalic acid. Particularly preferred are adipic acid, dodecanedioic acid, terephthalic acid and isophthalic acid.
• equimolar amounts of diamines and dicarboxylic acids can be used. If desired, one can also work with an excess of diamines or dicarboxylic acids. Often, a slight excess of diamines is used, as these are more volatile than the dicarboxylic acids and can occur in the process losses on diamines. By the separation of the vapor phase after the helical tube and recycling of the organic components in the polymerization monomer losses are largely avoided. Therefore, it is preferable to work in about stoichiometric range of diamines and dicarboxylic acids. Deviations of about 5%, preferably about 2.5%, in particular about 1% of the stoichiometry are possible according to the invention.
• aqueous solutions used generally have a content of 30 to 70 wt .-%, in particular 50 to 65 wt .-% of the salts mentioned.
• Aqueous solutions usually have a pH of 7.7 at 20 ° C.
• lactam in particular caprolactam
• an aqueous solution of (capro) lactam containing, for example, 60 to 90% by weight of (capro) lactam and by extraction of the copolyamide produced with water and evaporation of the aqueous extract, preferably with the addition of 0 , 5 to 2 times the amount of fresh lactam, based on extract lactam has been obtained.
• a suitable solution is obtained, for example, after in the DE-A 25 01 348 described method.
• the amount of salts of diamines and dicarboxylic acids, based on the total amount of monomer is preferably 0.2 to 40 mol%, particularly preferably 0.5 to 20 mol%.
• step a) an aqueous solution of lactams with salts of diamines and dicarboxylic acids under elevated pressure, which is greater than the vapor pressure of the resulting mixture, in a mixing apparatus at a temperature of 80 to 300 ° C, preferably 130 to 200 ° C, intensely mixed. It is preferred equimolar amounts of diamines and dicarboxylic acids used.
• elevated pressure is meant a pressure higher than normal pressure and the vapor pressure of the resulting mixture. Preference is given to working in a pressure range of 2.5 to 50 bar, preferably 5 to 20 bar.
• the mixing apparatus can be selected from any suitable mixing apparatus, in particular for liquids. These are preferably continuous mixers, in particular static mixers.
• the mixer installations can be chosen so that in the viscosity range of the monomer solutions as homogeneous as possible mixing takes place in a short time.
• an aqueous solution of salts of preferably equimolar amounts of diamines and dicarboxylic acids and lactam (s) is passed under elevated pressure and simultaneous evaporation of water through a helical tube evaporator to form a vapor phase and a liquid phase.
• the aqueous solution of salts of equimolar amounts of diamines and dicarboxylic acids and lactams are, if appropriate, premixed in a static mixer, depending on the desired Copolymerzusammen experience before they are introduced into the helical tube evaporator.
• the temperature in, preferably static, mixer is 80 to 300 ° C, preferably 130 to 200 ° C.
• water vapor and / or inert gas can be introduced into the mixture before the helical tube.
• Inert gas is z.
• nitrogen carbon dioxide or argon.
• the helical tube evaporator is preferably a double-walled tube, in which a heating medium is conducted in the heating jacket and serves for tempering.
• Technical double-jacket pipes which are preferably used according to the invention, have a length in the range from 20 to 100 m, more preferably 40 to 80 m, wherein they have an inner diameter of preferably 10 to 150 mm, in particular 15 to 60 mm.
• the helical tube evaporator causes in the aqueous solution of salts of equimolar amounts of diamines and dicarboxylic acids and lactams according to the invention a water evaporation, so that it comes to a volume expansion.
• a core flow through gas water vapor
• a wall film is present as a liquid phase.
• an inert gas can be added at the inlet or "head" of the helical tube, for example water vapor, N 2 , Ar, CO 2 or gas mixtures containing them, eg. B. 16 bar of water vapor to the core stream to create or amplify. This can be z. B. be necessary if not enough water in the aqueous solution of salts of diamines and equivalent amounts of dicarboxylic acid and caprolactam is present, for example, at total concentrations of the organic components above 98%.
• the added gas then serves as a carrier gas.
• a phase separation between the vapor phase and the liquid phase typically occurs.
• the core flow through the gas for example, based on the cross-sectional area of the helical tube make up an area fraction of 15 to 35%, in particular about 25%, while the wall film, ie, the liquid phase, 65 to 85%, in particular make up about 75% of the cross-sectional area.
• the helical tube evaporator can serve as a valve, since a high pressure, for example 5 to 20 bar, is present at the evaporator inlet, while the outlet of the reactor is at about atmospheric pressure. The pressure is thus reduced continuously over the length of the helical tube.
• the helical tube evaporator can as in WO 2008/049786 be described described.
• a temperature of 140 to 300 ° C, preferably 160 to 200 ° C, preferably 175 to 195 ° C is.
• there is a pressure reduction to about atmospheric pressure (1 bar) and a separation of a gaseous phase to obtain the liquid phase instead.
• the relaxation of the reaction mixture to about atmospheric pressure is thus carried out by passing through the helical tube.
• the gaseous phase contains predominantly water vapor, which is separated from the organic constituents after emerging from the helical tube evaporator.
• the vapor phase is removed via a column, wherein the column can be rinsed with water.
• the residence times are preferably in the range of 40 to 120 seconds. If longer residence times of 3 to 10 minutes are used, the helical tube evaporator is advantageously provided with internals, such as random packings, Raschig rings or Pall rings, in particular woven wire mesh rings, in order to achieve a large surface area.
• the two-phase mixture of vapor phase and liquid phase emerging from the helical tube consisting of salts of equimolar amounts of diamines and dicarboxylic acids and lactams or containing them, is subsequently separated.
• the separation usually occurs by itself due to the physical differences in a vessel.
• the two-phase mixture of vapor phase and liquid phase is passed into the vapor space at the head of the tubular polymerization zone of the vertical polymerization tube (VK tube) and carries out the separation there.
• the resulting vapor phase is separated in a column into steam, diamine, dicarboxylic acid and caprolactam, and all organic components are recycled to the polymerization in stage d).
• the separation of the vapor phase is advantageously carried out in a column under rectification. Suitable columns are, for example, packed columns, packed columns, bell, valve bottom or sieve tray columns with 5 to 15 theoretical plates.
• the column is conveniently under the identical conditions as in the separation of vapor phase and liquid phase, for. B. from 0.5 to 2.5 bar absolute or operated under the pressure of the polymerization.
• at the top of the column per kg of steam 0.1 to 0.5 l of water to improve the separation effect.
• the column effluent gives a liquid phase containing or consisting of diamines, dicarboxylic acids and lactams. At the top of the column falls to water vapor.
• liquid phase containing or consisting of diamines, dicarboxylic acids and lactams is passed back into the top of the VK tube.
• the organic phase from the helical tube containing or consisting of salts of diamines and (approximately) equivalent amounts of dicarboxylic acids and lactams and the reflux from the separation column are preferably mixed by stirring in the head of the vertical polymerization tube (VK tube).
• VK tube vertical polymerization tube
• the mixture of the VK tube head is passed from top to bottom through a vertical polymerization tube (VK tube) at polyamide-forming temperatures, and a copolyamide is obtained.
• VK tube vertical polymerization tube
• a copolyamide is obtained in the upper third of the polymerization.
• the melt is heated so that at the lower end of a melt with preferably 240 to 260 ° C. receives.
• the residence time in the polymerization tube is preferably 8 to 24 hours.
• the copolyamide thus obtained preferably has a relative viscosity of 2.0 to 3.0 and a content of extractable with water of 3.5 to 12 wt .-%, in particular 5 to 11 wt .-%.
• the copolyamide melt thus obtained is generally cast in strands, solidified and granulated or granulated directly by means of underwater granulation in a flowing stream of water. Suitable methods are known to the person skilled in the art.
• the granules thus obtained can then be extracted continuously in countercurrent with water at a temperature of preferably 80 to 120 ° C.
• the resulting aqueous extract is then advantageously after addition of 0.5 to 2 times the amount of fresh caprolactam, based on extract caprolactam, evaporated.
• a suitable method is described, for example in the DE-A 25 01 348 ,
• the extracted copolyamide is subsequently dried. It is advantageous in this case with the concomitant use of inert gases such as nitrogen or superheated steam as heat transfer in countercurrent to the desired viscosity, eg. B. at a temperature of 150 to 185 ° C, annealed.
• inert gases such as nitrogen or superheated steam
• Copolyamides obtainable by the process of the invention generally have from 60 to 99% by weight, in particular from 70 to 98% by weight, of polyamide 6 units and are suitable for the production of moldings by injection molding or extrusion, in addition to Production of threads, fibers and foils.
• the copolyamides of polyamide-6 and polyamide-6.6 units are prepared in a process sequence starting from 62% by weight aqueous AH saline solution and caprolactam.
• the AH saline solution is heated to 95 ° C and mixed with the separately heated to 200 ° C caprolactam in a static mixer.
• the mixture is passed at a pressure of about 9 bar and a temperature of about 180 ° C via a pressure control valve in a helical tube evaporator.
• water vapor is metered in at the inlet of the helical tube evaporator.
• the pressure at the entrance of the helical tube evaporator is about 5 bar.
• the steam is introduced to introduce energy into the monomer mixture and to blow the mixture through the subsequent helical tube.
• the helical tube evaporator is a double-walled tube, in which a heating medium is conducted in the heating jacket and serves for temperature control.
• the length is in the range of 20 to 100 m, and the inner diameter is preferably 15 to 60 mm.
• the evaporator tube is arranged according to a screw or helix.
• the helical tube evaporator causes a water evaporation in the aqueous mixture, so that it comes to a volume expansion.
• the pressure is continuously reduced via the helical tube evaporator.
• the spiral tube evaporator has high flow velocities, since a lot of steam is generated.
• the strong formation of steam leads to very short residence times and to self-cleaning of the helical tube.
• the mixture leaving the helical tube evaporator at a temperature of 195 ° C at about atmospheric pressure is fed to the top of a VK tube.
• At the top of the VK pipe there is a temperature of about 258 ° C.
• the vapor phase is separated off via a column at the top of the VK tube and discharged after condensation.
• the remaining monomer mixture passes through the VK tube which is heated in segments, with the temperature gradually decreasing towards the exit of the VK tube through the temperatures of 265 ° C and about 270 ° C to about 250 ° C at the exit of the VK tube ,
• the VK pipe is operated at the adjusting hydrostatic system pressure.
• a PA6 / 6.6 melt is obtained, which is fed via a discharge pump directly to a strand granulation or underwater granulation with subsequent extraction stage and then subsequent drying. The drying is followed by a postcondensation.
• the residence time in the helical tube evaporator is in the range of minutes, while the residence time in the CV tube is about 12 hours.
• the helical tube evaporator allows a gentler mixture and evaporation of water at low temperature, so that the thermal load of the monomer mixture is reduced.
• PA 6 / 6.6 copolymers of various relative viscosities were prepared in various production and experimental lines.
• the pressure was in the helical tube at 5 bar and the temperature at 195 ° C.
• the residence time was about one minute.
• the polymerization in the VK tube was carried out at a temperature of 240 to 290 ° C, a pressure of 300 m bar and a residence time of 12 hours.
• the in EP-A-0-393-546 used operating parameters described.
• the determination of the amino end groups and carboxyl end groups (AEG and CEG) was carried out according to the in WO 95/01389 , Page 6, line 35 to page 7, line 40 described method.
• the relative viscosity (RV) was determined at a temperature of 25 ° C and a concentration of 1 g of polymer per 100 ml in 96 wt .-% sulfuric acid.
• Table 1 below shows the compositions and the properties of the products.
• the PA 6.6 ratio was adjusted to give a melting point of 196 ° C for both technologies.
• the PA 6.6 content was adjusted so that a melting point of 192 ° C resulted.
• the PA 6.6 content was adjusted so that a melting point of 189 ° C resulted.
• Table 1 Summary of properties of the prepared PA 6 / 6.6 copolymers PA 6 / 6-6 copolymer relative viscosity melting point PA 6.6 Share AEG APHA number tkmax [-] [° C] [Wt .-%] [Mmol / kg] [-] [° C] invention 3.3 196 13.5 - 14.5 45.0 - 47.0 4 - 7 121-122 comparison 3.3 196 17.0 - 18.0 ⁇ 48 7 - 10 122 invention 4.0 189 17,5 - 18,5 36.5 - 38.5 6 - 8 118 comparison 4.0 192 18.5 - 19.5 ⁇ 40 8 - 10 118-128
• PA 6 / 6.6 copolymers produced by the technology according to the invention have a comparable PA 6.6 content have a much lower melting point of 189 ° C compared with 192 ° C.
• the 13 C NMR analyzes show the proportion of individual chemical bonds in the polymer chain. Of particular interest is the occurrence of direct chemical bonds between adipic acid (ADS) and hexamethylenediamine (HMD), which indicates the existence of PA6,6 block structures in the polymer chain.
• ADS adipic acid
• HMD hexamethylenediamine
• PA 6 / 6.6 copolymers prepared by the technology according to the invention also have a significantly lower proportion of PA 6.6 block structures at 3.2 mol% compared to 5 mol%.
• the advantages of the process according to the invention are thus independent of the viscosity of the final polymer.

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• 2009
  • 2009-12-09 ES ES09765113.7T patent/ES2632205T3/es active Active
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  • 2009-12-09 WO PCT/EP2009/066692 patent/WO2010066769A2/de active Application Filing
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